CN116120669A - Anti-drop high-stiffness file box material and preparation method thereof - Google Patents
Anti-drop high-stiffness file box material and preparation method thereof Download PDFInfo
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- CN116120669A CN116120669A CN202310284652.1A CN202310284652A CN116120669A CN 116120669 A CN116120669 A CN 116120669A CN 202310284652 A CN202310284652 A CN 202310284652A CN 116120669 A CN116120669 A CN 116120669A
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- 239000000463 material Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 polypropylene Polymers 0.000 claims abstract description 86
- 239000004743 Polypropylene Substances 0.000 claims abstract description 81
- 229920001155 polypropylene Polymers 0.000 claims abstract description 81
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 60
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 23
- 239000002667 nucleating agent Substances 0.000 claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 18
- 238000005469 granulation Methods 0.000 claims abstract description 18
- 230000003179 granulation Effects 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 12
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 229920005606 polypropylene copolymer Polymers 0.000 claims 1
- 230000002087 whitening effect Effects 0.000 abstract description 9
- 238000005266 casting Methods 0.000 description 30
- 238000012360 testing method Methods 0.000 description 22
- 239000000126 substance Substances 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 229920001903 high density polyethylene Polymers 0.000 description 7
- 239000004700 high-density polyethylene Substances 0.000 description 7
- 239000004595 color masterbatch Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 229920004934 Dacron® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 102220040412 rs587778307 Human genes 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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Abstract
The invention relates to a drop-resistant high-stiffness file box material and a preparation method thereof. According to the invention, part of polypropylene resin reacts with talcum powder, compatible compounding agent and part of antioxidant at high temperature to obtain talcum powder master batch of polypropylene grafted maleic anhydride, and then the talcum powder master batch of polypropylene grafted maleic anhydride, the rest of polypropylene resin, polyethylene resin, nucleating agent, lubricant and the rest of antioxidant are subjected to melt extrusion granulation to obtain the anti-drop high-stiffness file box material, so that the material has high strength and high toughness, maintains high modulus and high stiffness of the material, and avoids the problem of stress whitening.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an anti-falling high-stiffness file box material and a preparation method thereof.
Background
The file box can be divided into a paper file box and a plastic file box according to materials. The archives use paper archives box at a premium, and other scenes such as corporate offices and the like use plastic archives box at a premium. The paper file box is usually made of paperboards and kraft paper in pasting, is basically made of acid-free paper, can enable files to be stored for a long time, does not deteriorate and fade, and has the characteristics of insect prevention, mildew prevention and the like; the plastic file box is generally manufactured by casting high polymer materials such as polypropylene into sheets and then cutting, welding and the like.
The plastic file boxes currently used in the market generally use polypropylene as a matrix material, and because the polypropylene material has excellent processing performance, the polypropylene file boxes are various in shape, attractive and clean and convenient to use. However, the polypropylene file box has poor anti-falling performance, and when the file box falls from a desk with the height of 60cm, the diagonal folding position of the file box is easy to crack and break, so that the continuous use is influenced.
The utility model discloses a low-filling, high-modulus and high-toughness storage battery shell material with publication number CN 111621089A, and a preparation method and application thereofA material having a notched impact strength exceeding 50kJ/m 2 However, the toughener POE used in the method leads to higher material cost. The publication No. CN 108570191A discloses a material, namely a high-modulus high-toughness talcum powder filled polypropylene composite material and a preparation method thereof, wherein the material is subjected to filling modification by using talcum powder subjected to surface treatment, and the strength and toughness of the material can be improved simultaneously; the publication No. CN 104592632B, a high-toughness high-modulus polypropylene composite material and a preparation method thereof, discloses a material, which improves the strength and toughness of the material by means of the synergistic effect of boron nitride and titanium dioxide; however, both materials use the toughening agent POE, which not only has high manufacturing cost, but also has the notch impact strength of not more than 10kJ/m 2 It is difficult to maintain the high strength and high toughness of the material, and meanwhile, the high modulus and high stiffness characteristics are considered, the problem of stress whitening easily exists, and the requirement of the file box on drop and fracture resistance cannot be met.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a drop-resistant high-stiffness file box material which can improve the high strength and high toughness of the material, maintain the high modulus and high stiffness of the material and avoid the problem of stress whitening.
The second technical problem to be solved by the invention is to provide a preparation method of the anti-falling high-stiffness file box material aiming at the current state of the art.
The invention solves at least one of the technical problems by adopting the following technical proposal:
the anti-drop high-stiffness file box material comprises the following raw materials in percentage:
55 to 81.25 percent of polypropylene resin,
2.5 to 20 percent of polyethylene resin,
0.1 to 1 percent of nucleating agent,
xiang Rongfu, 0.15 to 0.9 percent of the mixture,
5 to 30 percent of mineral powder,
0.5 to 2 percent of lubricant,
0.4 to 0.6 percent of antioxidant;
the compatible compounding agent is a mixture of maleic anhydride and dicumyl peroxide.
In the invention, part of the polypropylene resin, talcum powder, compatible compounding agent and part of antioxidant react at high temperature to obtain talcum powder master batch of polypropylene grafted maleic anhydride, and the talcum powder master batch of polypropylene grafted maleic anhydride, the rest of the polypropylene resin, polyethylene resin, nucleating agent, lubricant and the rest of antioxidant are subjected to melt extrusion granulation to obtain the anti-drop high-stiffness file box material; in the high-temperature reaction process, the dicumyl peroxide takes polypropylene resin and mineral powder as reaction sites to initiate maleic anhydride to react. The mineral powder is micron-sized talcum powder, and polypropylene and talcum powder are chemically bridged together through maleic anhydride under the initiation of dicumyl peroxide. By adopting the mode, in the high-temperature reaction process, the dicumyl peroxide initiates the maleic anhydride to react, and the polypropylene and the talcum powder are taken as reaction sites, so that the produced talcum powder master batch of polypropylene grafted with the maleic anhydride has excellent compatibility through the chemical bridging action of the maleic anhydride, the cohesive force of the material and the talcum powder can be greatly improved, the uniform dispersion of the talcum powder can be promoted, the mechanical properties of the material can be improved, and the problem of stress whitening caused by poor compatibility of the talcum powder can be avoided. Preferably Ji Xiangteng maleic anhydride in chemical industry and dicumyl peroxide in the Guangzhou Sanming chemical industry.
Preferably, the talcum powder is of a multi-layered structure, and in the preparation process of the anti-falling high-stiffness file box material, the multi-layered structure of the talcum powder is broken into a single-layered structure and is subjected to infiltration treatment by the compatible compound agent. The talcum powder is of a lamellar structure, and the filling modification of the talcum powder can further improve the flexural modulus of the material and the stiffness of the sheet; the multi-lamellar structure of the talcum powder is scattered to form a single lamellar structure, and meanwhile, the compatible compound agent is added to infiltrate the surface of the talcum powder, so that the single lamellar layer of the talcum powder is promoted to be uniformly dispersed, the talcum powder is prevented from being agglomerated together again, and higher tensile strength and flexural modulus can be provided for the material.
Preferably, the talcum powder has a size of 5000-12500 meshes, D50 < 3 μm and whiteness of more than or equal to 98.
Preferably, the materials used for the anti-falling high-stiffness file box material comprise the following components in percentage:
64.95 to 73.3 percent of polypropylene resin,
polyethylene resin 5-20%,
0.1 to 0.3 percent of nucleating agent,
xiang Rongfu, 0.15 to 0.9 percent of the mixture,
10 to 30 percent of mineral powder,
1 to 1.5 percent of lubricant,
0.4 to 0.5 percent of antioxidant;
in the compatible compound agent, the mass ratio of maleic anhydride to dicumyl peroxide is 2:1.
Preferably, the polypropylene resin has a melt index of 1-10g/10min (230 ℃/2.16 kg) and a notched impact strength of 50-70kJ/m 2 High impact copolymer polypropylene of (a); preferably, the components are Yangzi petrochemical K8003 and Lanzhou petrochemical SP179. The notch impact strength of the high-impact polypropylene is very high, and the toughness can be provided for file boxes. The use of the high impact polypropylene can also avoid POE, so that the toughness of the material can be ensured, and the cost of the material can be greatly reduced. The polyethylene resin has a melt index of 0.5-1.5g/10min (190 ℃/2.16 kg) and a notched impact strength of 30-60kJ/m 2 Preferably middlemade HD5502 and bench-molded LH901. The high impact copolymer polypropylene resin contains a rubber phase, which is prone to stress whitening, and the file box produced by casting the sheet and made of the sheet is prone to whitening at folds. The molecular chains of HDPE and the molecular chains of the polypropylene are intertwined, so that the phenomenon of stress whitening can be relieved. Meanwhile, HDPE with high impact strength can also ensure high toughness of the final material.
Preferably, the nucleating agent is a phosphate nucleating agent; the nucleating agent can promote the nucleation and crystallization of polypropylene and polyethylene at the same time, so that the bending strength of the crystallized polypropylene and polyethylene is obviously improved, and the disadvantage of insufficient bending strength of the polypropylene and polyethylene resin is overcome. NA-20E, NA-11 or NA-21 of Italon is preferred. The lubricant is one or more of erucamide, ethylene bisstearamide, behenamide and oleamide; the lubricant is used for reducing the friction between the material and equipment during processing, reducing the friction coefficient between casting sheets and ensuring the surface brightness of the product; the antioxidants are a main antioxidant 1010 and an auxiliary antioxidant 168.
A preparation method of an anti-drop high-stiffness file box material comprises the following steps:
(1) Mixing part of granular polypropylene resin, talcum powder, compatible compounding agent and antioxidant by using a high-speed mixer, wherein the rotating speed is 1000-1500 rpm, the temperature is 70-90 ℃ and the time is 5-20 minutes, so as to obtain a mixture;
adding the mixture into a main feeding port of a double-screw extruder, wherein the rotating speed is 300-500 revolutions per minute, the reaction temperature is 180-220 ℃, preferably 190-210 ℃, carrying out melt extrusion granulation, and obtaining talcum powder master batch of polypropylene grafted maleic anhydride through water cooling and granulating;
(2) Adding talcum powder master batch of polypropylene grafted maleic anhydride, the rest polypropylene resin, polyethylene resin, nucleating agent, lubricant and antioxidant into a double-screw extruder through a main feeding port according to a proportion, wherein the rotating speed is 300-500 revolutions per minute, the reaction temperature is 180-220 ℃, preferably 190-210 ℃, carrying out melt extrusion granulation, and carrying out water cooling and granulating to obtain the anti-drop high-stiffness file box material.
The prepared file box material with high falling resistance and high stiffness is added into a casting machine, the processing temperature is 200-240 ℃, the thickness of a casting sheet is 0.8mm, and then the casting sheet is cut, welded and bound into a file box, and the prepared file box has the advantages of falling resistance, breakage resistance and high stiffness.
Preferably, the mass of the polypropylene resin used in the step (1) is 6 to 56% of the total mass of the polypropylene resin.
Compared with the prior art, the invention has the advantages that: according to the invention, part of polypropylene resin reacts with talcum powder, compatible compounding agent and part of antioxidant at high temperature to obtain talcum powder master batch of polypropylene grafted maleic anhydride, and then the talcum powder master batch of polypropylene grafted maleic anhydride, the rest of polypropylene resin, polyethylene resin, nucleating agent, lubricant and the rest of antioxidant are subjected to melt extrusion granulation to obtain the anti-drop high-stiffness file box material, so that the material has high strength and high toughness, maintains high modulus and high stiffness of the material, and avoids the problem of stress whitening.
Drawings
FIG. 1 is a SEM sectional view of a file box material according to example 1 of the present invention;
FIG. 2 is a SEM sectional view of the material of the file box according to comparative example 1.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
The raw materials for preparing the anti-drop high-stiffness file box material provided by the embodiment of the invention are as follows:
polypropylene: k8003, melt index 2-3g/10min (230 ℃,2.16 kg), flexural modulus 950-1050MPa, notched impact strength 55-65kJ/m 2 Purchased from chinese petrochemical, yang, petrochemical, inc;
polypropylene: SP179, melt index 9-10g/10min (230 ℃,2.16 kg), flexural modulus 1000-1100MPa, notched impact strength 50-55kJ/m 2 Purchased from chinese petroleum lanzhou petrochemical company;
polyethylene: HD5502, melt index of 0.3-0.5g/10min (190 ℃,2.16 kg), flexural modulus 1180MPa, notched impact strength of 34kJ/m 2 Purchased from the middle (guangdong) refining company, inc;
polyethylene: LH901, melt index of 0.9-1.0g/10min (190 ℃,2.16 kg), flexural modulus of 1100MPa, notched impact strength of 55kJ/m 2 Purchased from a station plastic group;
nucleating agent: NA-20E, melting point 210 ℃, purchased from Itai Long Yitai Dacron (Tianjin) synthetic materials Co., ltd;
nucleating agent: NA-11, melting point 508 ℃, purchased from Itai Long Yitai Dacron (Tianjin) synthetic materials Co., ltd;
nucleating agent: NA-21, melting point 210 ℃, purchased from Italon (Tianjin) synthetic materials Co., ltd;
compatible compounding agent: maleic anhydride with purity more than or equal to 99.5%, melting point 51-56 ℃ and Ji Xiangteng reaching chemical industry; dicumyl peroxide with purity not less than 99.5%, melting point 41-42 ℃ purchased from Guangzhou Sanming chemical industry Co., ltd;
talc powder: d50 is less than or equal to 3 mu m, the whiteness is more than or equal to 98, and the product is purchased from Liaoning Ai Hai talcum Co., ltd;
erucamide: purchased from cereal chemicals (Shanghai) limited;
oleic acid amide: purchased from cereal chemicals (Shanghai) limited;
ethylene bis-stearamide: purchased from cereal chemicals (Shanghai) limited;
behenic acid amide: purchased from cereal chemicals (Shanghai) limited;
and (3) a main antioxidant: 1010, purchased from xiu chemical Co., ltd;
auxiliary antioxidant: 168 purchased from xiu chemical Co., ltd;
color master batch: blue, purchased from Ningbo masterbatch Co.
The materials obtained in each example and comparative example were subjected to functional testing, and the main test methods involved were as follows:
(1) Tensile strength: testing the tensile strength of the sample bar by adopting a double-upright universal testing machine according to GB/T1040.3;
(2) Flexural modulus: testing the flexural modulus of the sample bar by adopting a double-upright universal testing machine according to GB/T9341-2008;
(3) Notched impact strength: testing the notch impact strength of the cantilever beam of the spline according to GB/T1843-2008 by adopting a full-automatic notch machine;
(4) Limit drop height: the diagonal line of the file box is perpendicular to the ground, the back of the file box is close to the wall surface, the file box is released to freely fall down to the cement ground, the height from the ground, which is the lowest of the diagonal line of the file box, is recorded as the falling height, and the falling height without damage of the file box is the limit falling height;
(5) Appearance: observing whether the folding and welding parts of the file box have blushing phenomena.
Example 1:
the preparation method of the anti-falling high-stiffness file box material in the embodiment comprises the following steps of:
1) 500g of talcum powder, 500g of polypropylene K8003, 10g of maleic anhydride, 5g of dicumyl peroxide, 2g of main antioxidant 1010 and 2g of auxiliary antioxidant 168 are added into a high-speed mixer to be mixed, the rotating speed is 1300 revolutions per minute, the temperature is 80 ℃, and the reaction time is 10 minutes, so as to obtain a mixture; adding the mixture into a main feeding port of an extruder, wherein the rotating speed is 300 revolutions per minute, the reaction temperature is 180 ℃, performing melt extrusion granulation, and obtaining talcum powder master batch of polypropylene grafted maleic anhydride through water cooling and granulating;
2) The talcum powder master batch of the polypropylene grafted maleic anhydride, 6540g of polypropylene K8003, 2000g of polyethylene HD5502, 5g of nucleating agent NA-20E, 200g of erucamide, 18g of primary antioxidant 1010, 18g of secondary antioxidant 168 and 200g of color master batch are added into a double-screw extruder through a primary feeding port, the rotating speed is 300 r/min, the reaction temperature is 180 ℃, melt extrusion granulation is carried out, and the anti-drop high-stiffness archival box material is obtained through water cooling and granulating.
The above materials were injection molded into standard tensile, flexural and impact bars, and allowed to stand at 23℃in an environment of 50% humidity for 48 hours, followed by testing for tensile, flexural and impact properties. The above materials are added into a casting machine, the processing temperature is 220 ℃, the thickness of a casting sheet is 0.8mm, then the casting sheet is cut, welded and bound into a file box, the file box is stood for 48 hours in an environment with the temperature of 23 ℃ and the humidity of 50%, and then the limit drop height is tested. The test results are shown in Table 1.
Example 2:
the preparation method of the anti-falling high-stiffness file box material in the embodiment comprises the following steps of:
1) 1000g of talcum powder, 1000g of polypropylene K8003, 10g of maleic anhydride, 5g of dicumyl peroxide, 4g of main antioxidant 1010 and 4g of auxiliary antioxidant 168 are added into a high-speed mixer to be mixed, the rotating speed is 1400 r/min, the temperature is 90 ℃, and the reaction time is 15 min, so as to obtain a mixture; adding the mixture into a main feeding port, wherein the rotating speed is 450 revolutions per minute, the reaction temperature is 200 ℃, carrying out melt extrusion granulation, and obtaining talcum powder master batch of polypropylene grafted maleic anhydride through water cooling and granulating;
2) Adding talcum powder master batch of polypropylene grafted maleic anhydride, 7125g of polypropylene SP179, 500g of high-density polyethylene LH901, 10g of nucleating agent NA-11, 100g of oleamide, 26g of main antioxidant 1010, 16g of auxiliary antioxidant 168 and 200g of color master batch into a double-screw extruder through a main feeding port, carrying out melt extrusion granulation at the reaction temperature of 200 ℃ at the rotation speed of 450 r/min, and carrying out water cooling and granulating to obtain the anti-drop high-stiffness archival box material.
The above materials were injection molded into standard tensile, flexural and impact bars, and allowed to stand at 23℃in an environment of 50% humidity for 48 hours, followed by testing for tensile, flexural and impact properties. The above materials are added into a casting machine, the processing temperature is 220 ℃, the thickness of a casting sheet is 0.8mm, then the casting sheet is cut, welded and bound into a file box, the file box is stood for 48 hours in an environment with the temperature of 23 ℃ and the humidity of 50%, and then the limit drop height is tested. The test results are shown in Table 1.
Example 3:
the preparation method of the anti-falling high-stiffness file box material in the embodiment comprises the following steps of:
1) Adding 1500g of talcum powder, 1500g of polypropylene K8003, 60g of maleic anhydride, 30g of dicumyl peroxide, 6g of main antioxidant 1010 and 6g of auxiliary antioxidant 168 into a high-speed mixer for mixing, wherein the rotating speed is 1000 revolutions per minute, the temperature is 70 ℃, and the reaction time is 5 minutes, so as to obtain a mixture; adding the mixture into a main feeding port of an extruder, wherein the rotating speed is 500 revolutions per minute, the reaction temperature is 190 ℃, performing melt extrusion granulation, and obtaining talcum powder master batch of polypropylene grafted maleic anhydride through water cooling and granulating;
2) The talcum powder master batch of the polypropylene grafted maleic anhydride, 4995g of polypropylene K8003, 1500g of high-density polyethylene HD5502, 15g of nucleating agent NA-21, 150g of behenic acid amide, 14g of primary antioxidant 1010, 24g of secondary antioxidant 168 and 200g of color master batch are added into a double screw extruder through a primary feeding port, the reaction temperature is 190 ℃, melt extrusion granulation is carried out, and the anti-drop high-stiffness file box material is obtained through water cooling and granulating.
The above materials were injection molded into standard tensile, flexural and impact bars, and allowed to stand at 23℃in an environment of 50% humidity for 48 hours, followed by testing for tensile, flexural and impact properties. The above materials are added into a casting machine, the processing temperature is 220 ℃, the thickness of a casting sheet is 0.8mm, then the casting sheet is cut, welded and bound into a file box, the file box is stood for 48 hours in an environment with the temperature of 23 ℃ and the humidity of 50%, and then the limit drop height is tested. The test results are shown in Table 1.
Example 4:
the preparation method of the anti-falling high-stiffness file box material in the embodiment comprises the following steps of:
1) 2000g of talcum powder, 2000g of polypropylene SP179, 60g of maleic anhydride, 30g of dicumyl peroxide, 8g of main antioxidant 1010 and 8g of auxiliary antioxidant 168 are added into a high-speed mixer to be mixed, the rotating speed is 1500 revolutions per minute, the temperature is 75 ℃, and the reaction time is 20 minutes, so as to obtain a mixture; adding the mixture into a main feeding port of an extruder, wherein the rotating speed is 400 rpm, the reaction temperature is 220 ℃, performing melt extrusion granulation, and performing water cooling and granulating to obtain talcum powder master batch of polypropylene grafted maleic anhydride;
2) Adding talcum powder master batch of polypropylene grafted maleic anhydride, 5330g of polypropylene SP179, 250g of high-density polyethylene LH901, 20g of nucleating agent NA-11, 50g of ethylene bis-stearamide, 22g of main antioxidant 1010, 22g of auxiliary antioxidant 168 and 200g of color master batch into a double-screw extruder through a main feeding port, carrying out melt extrusion granulation at the reaction temperature of 220 ℃ at the rotation speed of 400 rpm, and carrying out water cooling and granulating to obtain the anti-drop high-stiffness file box material.
The above materials were injection molded into standard tensile, flexural and impact bars, and allowed to stand at 23℃in an environment of 50% humidity for 48 hours, followed by testing for tensile, flexural and impact properties. The above materials are added into a casting machine, the processing temperature is 220 ℃, the thickness of a casting sheet is 0.8mm, then the casting sheet is cut, welded and bound into a file box, the file box is stood for 48 hours in an environment with the temperature of 23 ℃ and the humidity of 50%, and then the limit drop height is tested. The test results are shown in Table 1.
Example 5:
the preparation method of the anti-falling high-stiffness file box material in the embodiment comprises the following steps of:
1) Adding 3000g of talcum powder, 3000g of polypropylene K8003, 40g of maleic anhydride, 20g of dicumyl peroxide, 12g of main antioxidant 1010 and 12g of auxiliary antioxidant 168 into a high-speed mixer for mixing, wherein the rotating speed is 1200 revolutions per minute, the temperature is 85 ℃, and the reaction time is 15 minutes, so as to obtain a mixture; adding the mixture into a main feeding port of an extruder, wherein the rotating speed is 350 revolutions per minute, the reaction temperature is 210 ℃, performing melt extrusion granulation, and obtaining talcum powder master batch of polypropylene grafted maleic anhydride through water cooling and granulating;
2) The talcum powder master batch of the polypropylene grafted maleic anhydride, 2500g of polypropylene K8003, 1000g of high-density polyethylene HD5502, 30g of nucleating agent NA-21, 150g of erucamide, 8g of primary antioxidant 1010, 28g of secondary antioxidant 168 and 200g of color master batch are added into a double-screw extruder through a primary feeding port, the rotating speed is 350 r/min, the reaction temperature is 210 ℃, melt extrusion granulation is carried out, and the anti-drop high-stiffness archival box material is obtained through water cooling and granulating.
The above materials were injection molded into standard tensile, flexural and impact bars, and allowed to stand at 23℃in an environment of 50% humidity for 48 hours, followed by testing for tensile, flexural and impact properties. The above materials are added into a casting machine, the processing temperature is 220 ℃, the thickness of a casting sheet is 0.8mm, then the casting sheet is cut, welded and bound into a file box, the file box is stood for 48 hours in an environment with the temperature of 23 ℃ and the humidity of 50%, and then the limit drop height is tested. The test results are shown in Table 1.
Comparative example 1
10g of maleic anhydride and 5g of dicumyl peroxide were removed in example 1, and the other conditions were unchanged.
The above materials were injection molded into standard tensile, flexural and impact bars, and allowed to stand at 23℃in an environment of 50% humidity for 48 hours, followed by testing for tensile, flexural and impact properties. The above materials are added into a casting machine, the processing temperature is 220 ℃, the thickness of a casting sheet is 0.8mm, then the casting sheet is cut, welded and bound into a file box, the file box is stood for 48 hours in an environment with the temperature of 23 ℃ and the humidity of 50%, and then the limit drop height is tested. The test results are shown in Table 1.
Comparative example 2
The polypropylene K8003 of example 1 was changed to polypropylene T30S, and the other conditions were unchanged.
The above materials were injection molded into standard tensile, flexural and impact bars, and allowed to stand at 23℃in an environment of 50% humidity for 48 hours, followed by testing for tensile, flexural and impact properties. The above materials are added into a casting machine, the processing temperature is 220 ℃, the thickness of a casting sheet is 0.8mm, then the casting sheet is cut, welded and bound into a file box, the file box is stood for 48 hours in an environment with the temperature of 23 ℃ and the humidity of 50%, and then the limit drop height is tested. The test results are shown in Table 1.
[ comparative example 3 ]
500g of the high-density polyethylene LH901 from example 2 was replaced with 500g of the linear low-density polyethylene 7042, all other conditions being unchanged.
The above materials were injection molded into standard tensile, flexural and impact bars, and allowed to stand at 23℃in an environment of 50% humidity for 48 hours, followed by testing for tensile, flexural and impact properties. The above materials are added into a casting machine, the processing temperature is 220 ℃, the thickness of a casting sheet is 0.8mm, then the casting sheet is cut, welded and bound into a file box, the file box is stood for 48 hours in an environment with the temperature of 23 ℃ and the humidity of 50%, and then the limit drop height is tested. The test results are shown in Table 1.
Table 1 characterization of drop-resistant high stiffness archival box materials and archival box effects prepared in examples and comparative examples
In addition, comparing the SEM cross-sectional profiles of fig. 1 and 2, it can be seen from fig. 1 that the whole cross-section is more complete, wherein less volume of the flake talc is exposed on the cross-section; as can be seen from fig. 2, the cross section has a significant crack, wherein the flake-like talc is significantly exposed on the cross section. The results prove that after the dicumyl peroxide initiates the maleic anhydride to react, the polypropylene and the talcum powder are chemically bridged by the maleic anhydride, so that the compatibility between the talcum powder and the polypropylene is increased, the strength and the toughness of the material can be improved, and the problem of stress whitening caused by poor compatibility of the talcum powder can be avoided.
Claims (10)
1. An anti-drop high-stiffness file box material is characterized in that: the raw materials adopted by the method comprise the following components in percentage by weight
55 to 81.25 percent of polypropylene resin,
2.5 to 20 percent of polyethylene resin,
0.1 to 1 percent of nucleating agent,
xiang Rongfu, 0.15 to 0.9 percent of the mixture,
5 to 30 percent of mineral powder,
0.5 to 2 percent of lubricant,
0.4 to 0.6 percent of antioxidant;
the compatible compounding agent is a mixture of maleic anhydride and dicumyl peroxide.
2. The drop-resistant high stiffness file box material of claim 1, wherein: part of the polypropylene resin, talcum powder, compatible compounding agent and part of antioxidant react at high temperature to obtain talcum powder master batch of polypropylene grafted maleic anhydride, and the talcum powder master batch of polypropylene grafted maleic anhydride, the rest of the polypropylene resin, polyethylene resin, nucleating agent, lubricant and the rest of antioxidant are subjected to melt extrusion granulation to obtain the anti-falling high-stiffness file box material; in the high-temperature reaction process, the dicumyl peroxide takes polypropylene resin and mineral powder as reaction sites to initiate maleic anhydride to react.
3. The drop-resistant high stiffness file box material of claim 2, wherein: the mineral powder is micron-sized talcum powder, and polypropylene and talcum powder are chemically bridged together through maleic anhydride under the initiation of dicumyl peroxide.
4. A drop-resistant high stiffness file box material as in claim 3, wherein: the talcum powder is of a multi-layered structure, and in the preparation process of the anti-falling high-stiffness file box material, the multi-layered structure of the talcum powder is broken into a single-layered structure and is subjected to infiltration treatment by the compatible compound agent.
5. A drop-resistant high stiffness file box material as in claim 3, wherein: the size of the talcum powder is 5000-12500 meshes, D50 is less than 3 mu m, and the whiteness is more than or equal to 98.
6. The drop-resistant high stiffness file box material of any one of claims 1 to 5, wherein: the raw materials adopted by the method comprise the following components in percentage by weight
64.95 to 73.3 percent of polypropylene resin,
polyethylene resin 5-20%,
0.1 to 0.3 percent of nucleating agent,
xiang Rongfu, 0.15 to 0.9 percent of the mixture,
10 to 30 percent of mineral powder,
1 to 1.5 percent of lubricant,
0.4 to 0.5 percent of antioxidant;
in the compatible compound agent, the mass ratio of maleic anhydride to dicumyl peroxide is 2:1.
7. The drop-resistant high stiffness file box material of any one of claims 1 to 5, wherein: the polypropylene resin has a melt index of 1-10g/10min and a notched impact strength of 50-70kJ/m 2 Is a polypropylene copolymer; the polyethylene resin has a melt index of 0.5-1.5g/10min and a notched impact strength of 30-60kJ/m 2 Is a polyethylene resin of (a).
8. The drop-resistant high stiffness file box material of any one of claims 1 to 5, wherein: the nucleating agent is phosphate nucleating agent; the lubricant is one or more of erucamide, ethylene bisstearamide, behenamide and oleamide; the antioxidants are a main antioxidant 1010 and an auxiliary antioxidant 168.
9. The preparation method of the anti-drop high-stiffness file box material is characterized by comprising the following steps of:
(1) Mixing part of granular polypropylene resin, talcum powder, compatible compounding agent and part of antioxidant by using a high-speed mixer, wherein the rotating speed is 1000-1500 rpm, the temperature is 70-90 ℃ and the time is 5-20 minutes, so as to obtain a mixture;
adding the mixture into a main feeding port of a double-screw extruder, wherein the rotating speed is 300-500 revolutions per minute, the reaction temperature is 180-220 ℃, carrying out melt extrusion granulation, and obtaining talcum powder master batch of polypropylene grafted maleic anhydride through water cooling and granulating;
(2) Adding talcum powder master batch of polypropylene grafted maleic anhydride, the rest polypropylene resin, polyethylene resin, nucleating agent, lubricant and the rest antioxidant into a double-screw extruder through a main feeding port according to a proportion, wherein the rotating speed is 300-500 revolutions per minute, the reaction temperature is 180-220 ℃, carrying out melt extrusion granulation, and carrying out water cooling and granulating to obtain the anti-drop high-stiffness file box material.
10. The method for preparing the anti-drop high stiffness file box material according to claim 9, wherein the method comprises the following steps: the mass of the polypropylene resin used in the step (1) is 6-56% of the total mass of the polypropylene resin.
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